KR102308626B1 - Coating composition for protecting tree and wood and for controlling plant disease and insect pest - Google Patents

Abstract

The present invention relates to a coating composition for protecting trees and woods and for controlling pests. The coating composition for protecting trees and woods and for controlling pests of the present invention is capable of preventing damage to trees due to climatic disasters, making a wound in a tree heal faster, helping the growth of trees, and protecting trees and woods from pests and diseases. The coating composition for protecting trees and woods and for controlling pests comprises with respect to 100 wt% of an aged essence of Ginkgo biloba: 10-30 wt% of a yeast fermented product of Ginkgo biloba flesh layer, leaves and barks of Ginkgo biloba; 10-30 wt% of a pyroligneous liquor; and 5-25 wt% of titanium dioxide powder.

Description

Coating composition for protecting tree and wood and for controlling plant disease and insect pest}

The present invention can prevent damage to trees due to climatic disasters, urgently restore the wounds of trees, help the growth of trees, and protect trees and trees that can protect trees and trees from pests and diseases. It relates to a coating composition for controlling pests.

The growth of trees is greatly affected by external environmental changes and stress, and the defect rate of trees is increasing due to recent climate change. Recently, the average temperature is gradually increasing and the occurrence of abnormal climates is increasing, and damage to tree growth due to climatic disasters such as summer heat waves and torrential rain is increasing. More specifically, the East Sea and Wind Damage of Fruit Trees, Trees and Flowers due to the unusually low temperature in spring; damage from sun exposure due to unusually high temperatures in summer, frequent typhoons, strong winds and heavy rain; The unusually low temperature and heavy snow damage in winter put a great burden on farms.

On the other hand, in Korea, where more than 60% of the country is made up of forests, it is known that there are 2,600 kinds of recorded pests (Kwang-Sik Choi, Pest Encyclopedia of Special Trees, Research Report No. 24, 2007). In particular, the quality of life such as walnuts and jujubes, which are fruit trees cultivated to increase the income of farmers, has improved, and interest in landscape trees, garden trees, and bonsai trees is increasing, but these trees are being damaged by pests. Pests that injure trees mainly include aphids, which are succulent pests that suck leaves, and lepidoptera, which are leaf-eating pests that eat shield beetles and leaves. Insects can be easily controlled by spraying chemicals. However, it is impossible to control the perforating pests such as sky oxen, tree moths, and bat moths, which inflict damage on the woody part of trees, by spraying chemicals. In addition, the damage caused by powdery wood moths, wood moths, and termites, which injure wood products such as wood construction materials and wood furniture, is also increasing day by day.

Accordingly, the need for technology development that can prevent damage to trees caused by climate disasters, restore the scars of trees, and help the growth of trees, as well as protect trees and trees from pests and pests is emerging. have.

Republic of Korea Patent No. 10-1313003 Republic of Korea Patent No. 10-2047931

The present invention has been devised to solve the above-described problems, and an embodiment of the present invention can prevent damage to a tree due to a climate disaster, urgently restore a scar on the tree, and help the growth of the tree. Rather, it is an object of the present invention to provide a coating composition for protection of trees and wood that can protect trees and wood from pests and pests and for controlling pests.

Various problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

One embodiment of the present invention is based on 100 parts by weight of the aged ginkgo extract, 10 to 30 parts by weight of the yeast fermented product of the flesh layer of ginkgo berries, ginkgo leaves and ginkgo bark; 10 to 30 parts by weight of wood vinegar; and 5 to 25 parts by weight of titanium dioxide powder as a coating composition for protection of trees and wood and pest control,

The aged ginkgo extract is prepared by placing ginkgo in a hot-pressurized extractor, purifying the hot water solution obtained by boiling at 110 to 250 ° C. for 60 to 72 hours, then distilling and cooling the ginkgo extract; and aging the prepared ginkgo extract at 20 to 25° C. for 3 to 6 months to prepare a ginkgo aged extract;

The yeast fermented product of the flesh layer of the ginkgo biloba, ginkgo leaves and ginkgo bark is obtained by collecting the flesh layer of the ginkgo berry, raw ginkgo leaves and ginkgo bark from the ginkgo tree, steaming and drying the ginkgo berry flesh layer, ginkgo leaves and ginkgo biloba. pretreatment of the peel; After mixing 1 to 5 times the weight of water with the pre-treated ginkgo meat layer, ginkgo leaves and ginkgo bark, it is heated at 110 to 180 ° C for 1 to 3 hours to extract the ginkgo meat layer, ginkgo leaves and ginkgo biloba. skin extract preparation step; Inoculating yeast mold in a liquid medium in which bran and glucose solution are mixed with the flesh layer of the ginkgo berry, ginkgo leaf and ginkgo bark extract, and culturing at 25 to 35° C. for 5 to 10 days; And after mixing a sodium phosphate buffer solution with a culture containing the extract of the flesh layer of ginkgo biloba, ginkgo leaves and ginkgo bark extract, filtration and centrifugation to obtain a supernatant, so that the yeast fermentation of the flesh layer of ginkgo biloba, ginkgo leaves and ginkgo bark It provides a coating composition for the protection and pest control of trees and wood that is prepared by a manufacturing method comprising; preparing water.

The aged ginkgo extract is a mixture of the prepared ginkgo extract and gelatin-apatite sol in a weight ratio of 1: 0.1 to 3, after the step of preparing the ginkgo extract, and aged at 20 to 25 ° C. for 3 to 6 months. It is to be prepared by a manufacturing method comprising the step of preparing the aged ginkgo juice;

The gelatin-apatite sol is prepared by precipitating _{Ca(NO 3} ) ₂ .4H ₂ O and (NH ₃ ) ₂ HPO ₄ so that the molar ratio of [Ca]/[P] in gelatin is in the range of 0.5 to 0.9. it could be

The wood vinegar is a step of carbonizing the trees by applying a temperature of 800 to 1,000 ℃ after inputting 50 to 60% by weight of oak and 40 to 50% by weight of chrysanthemum wood in a loess kiln; When the smoke discharged through the flue of the loess kiln turns white, closing the kiln entrance leaving only a small vent; a liquefaction step of collecting and cooling the smoke emitted when the temperature of the flue reaches 85 to 120 °C; A step of aging the crude wood vinegar collected by liquefying the smoke in a container for at least one year at room temperature; And removing the sediment and suspended matter of the aged crude wood vinegar and filtering it with a filter to prepare an acidic wood vinegar of pH 3.5 to 4.5; it may be prepared by a manufacturing method comprising a.

The coating composition for tree and wood protection and pest control may further include 1 to 5 parts by weight of water-dispersed sulfur and 0.1 to 2 parts by weight of silicoaluminophosphate with respect to 100 parts by weight of the aged ginkgo extract.

The water-dispersed sulfur is 1 to 10% by weight of sulfur monomers generated in the refining process of crude oil, 1 to 10% by weight of an aliphatic polyester-based polymer, and 50 to 80% by volume of an organic phase containing the remaining amount of an organic solvent, and ammonium (bi) 5 to 30% by weight of an effervescent salt of carbonate or sodium carbonate and 20 to 50% by volume of a first aqueous phase containing the remaining amount of distilled water to obtain a uniform W/O emulsion; and mixing the W / O emulsion with a second aqueous phase containing 0.1 to 0.5 wt % of a hydrophilic surfactant and the remaining amount of distilled water in a 1: 10 to 20 volume ratio, emulsifying, and then electrolyzing. prepared by;

The silicoaluminophosphate is synthesized by dissolving a block copolymer of polyethylene oxide and polypropylene oxide in an organic solvent containing alcohol to synthesize a first template solution; synthesizing a second template solution by dissolving piperidine and tetramethylammonium chloride (TMACl) in distilled water; In 100 parts by weight of a mixed template solution obtained by mixing the first template solution and the second template solution in a ratio of 1: 2 to 5 by weight, sodium silicate, pseudo-bohemite, and alkylphosphos represented by the following Chemical Formula 1 Preparing a hydrogel by mixing 20 to 50 parts by weight of a source mixture in which the phonic acid compound is mixed in an amount of 50 to 80% by weight, 15 to 45% by weight, and 1 to 10% by weight, respectively; Forming a solid product by stirring the prepared hydrogel at a temperature of 30 to 90 ℃ for 2 to 24 hours and then stirring for 5 to 48 hours at a temperature of 150 to 200 ℃ for hydrothermal reaction; and calcining the obtained solid product at a temperature of 800 to 1000 °C for 1 to 5 hours at a temperature increase rate of 0.2 to 2 °C/min, followed by slow cooling.

[Formula 1]

In the above formula, R ¹ is a linear or branched C1 to C4 alkyl group, and x is 0 or 1.

According to the coating composition for protection of trees and wood and pest control according to an embodiment of the present invention, it provides a buffer insulation effect to trees and wood, so that external conditions such as abnormal low temperature in spring and winter and abnormal high temperature in summer It has the effect of preventing damage to trees due to climatic disasters caused by excessive temperature changes.

In addition, there is an effect that can protect the trees and wood by applying directly to the trees and wood. In particular, in the case of trees, it is possible to promote the growth of trees by inhibiting moisture evaporation by forming a protective film, and by promoting wound healing and regeneration, it has the effect of urgently restoring the wounds of trees and helping the growth of trees. .

In addition, by providing a protective film having excellent adhesion and durability, there is an effect of providing a coating film having a low loss rate of the coating film due to environmental changes after application and high stability.

In addition, the repelling effect of various pests, including silverfish, cockroaches, rice beetles, ants, mites, etc., is excellent, and this repelling effect is maintained for a long period of time, thereby protecting trees and wood from pests. In particular, unlike existing coating agent compositions, it is harmless to the human body and eco-friendly, so it is applied directly to not only domestic wood, but also various parks and city living facilities made of wood, and plantings such as street trees and fruit trees to create a comfortable indoor and outdoor environment. can have an effect.

Hereinafter, embodiments of the present invention will be described in detail. However, this is provided as an example, and the present invention is not limited thereto, and the present invention is only defined by the scope of the claims to be described later.

One embodiment of the present invention is based on 100 parts by weight of the aged ginkgo extract, 10 to 30 parts by weight of the yeast fermented product of the flesh layer of ginkgo berries, ginkgo leaves and ginkgo bark; 10 to 30 parts by weight of wood vinegar; And it relates to a coating composition for protection of trees and wood and pest control comprising 5 to 25 parts by weight of titanium dioxide powder.

At this time, the aged ginkgo extract is prepared by placing ginkgo biloba in a hot-pressurized extractor, purifying the hot water solution obtained by boiling at 110 to 250 ° C. for 60 to 72 hours, then distilling and cooling the ginkgo biloba extract; And the prepared ginkgo extract is aged at 20 to 25 ℃ for 3 to 6 months to prepare the aged ginkgo extract; what is prepared by a manufacturing method comprising a can be preferably used.

In addition, the yeast fermented product of the flesh layer of ginkgo biloba, ginkgo leaves and ginkgo bark is obtained by collecting the flesh layer of ginkgo biloba, raw ginkgo leaves and ginkgo bark from the ginkgo tree, steaming and drying the ginkgo berry flesh layer, ginkgo leaves and pretreatment step of ginkgo bark; After mixing 1 to 5 times the weight of water with the pre-treated ginkgo meat layer, ginkgo leaves and ginkgo bark, it is heated at 110 to 180 ° C for 1 to 3 hours to extract the ginkgo meat layer, ginkgo leaves and ginkgo biloba. skin extract preparation step; Inoculating yeast mold in a liquid medium in which bran and glucose solution are mixed with the flesh layer of the ginkgo berry, ginkgo leaf and ginkgo bark extract, and culturing at 25 to 35° C. for 5 to 10 days; And after mixing a sodium phosphate buffer solution with a culture containing the extract of the flesh layer of ginkgo biloba, ginkgo leaves and ginkgo bark extract, filtration and centrifugation to obtain a supernatant, so that the yeast fermentation of the flesh layer of ginkgo biloba, ginkgo leaves and ginkgo bark What is prepared by a manufacturing method comprising; preparing water can be preferably used.

According to the coating composition for protection and pest control of trees and wood according to one embodiment of the present invention, it provides a buffer insulation effect to trees and wood, and external such as abnormal low temperature phenomenon in spring and winter and abnormal high temperature phenomenon in summer It has the effect of preventing damage to trees due to climatic disasters caused by excessive temperature changes.

In addition, there is an effect that can protect the trees and wood by applying directly to the trees and wood. In particular, in the case of trees, it is possible to promote the growth of trees by inhibiting moisture evaporation by forming a protective film, and by promoting wound healing and regeneration, it has the effect of urgently restoring the wounds of trees and helping the growth of trees. .

In addition, by providing a protective film having excellent adhesion and durability, there is an effect of providing a coating film having a low loss rate of the coating film due to environmental changes after application and high stability.

In addition, the repelling effect of various pests, including silverfish, cockroaches, rice beetles, ants, mites, etc., is excellent, and this repelling effect is maintained for a long period of time, thereby protecting trees and wood from pests. In particular, unlike existing coating agent compositions, it is harmless to the human body and eco-friendly, so it is applied directly to not only domestic wood, but also various parks and city living facilities made of wood, and plantings such as street trees and fruit trees to create a comfortable indoor and outdoor environment. can have an effect.

More specifically, the aged ginkgo extract provides excellent film adhesion and durability; It functions to provide the effect of restoring the wounds of trees, promoting the growth of trees, and providing excellent repelling effects of pests and diseases.

The aging ginkgo extract is prepared by placing ginkgo biloba in a hot press extractor, purifying the hot water solution obtained by boiling at 110 to 250° C. for 60 to 72 hours, then distilling and cooling the ginkgo biloba extract; And the prepared ginkgo extract is aged at 20 to 25 ℃ for 3 to 6 months to prepare the aged ginkgo extract; what is prepared by a manufacturing method comprising a can be preferably used.

The part of the ginkgo biloba may be one or more parts selected from stems, branches, bark and roots, and more preferably a stem, but is not limited thereto.

It is possible to extract the essence of the material by extracting under pressure at high temperature by adding only ginkgo biloba without adding water to the hot press extractor. This has the effect of extracting high-quality essence with high efficiency by using the hot water method. Conventional hot water and solvent extraction method had a problem of low extraction efficiency because only a very small amount of active ingredient was extracted from ginkgo, and the method of extracting by applying heat directly to the tree had problems such as burnt odor and component destruction. is a very effective complement to the problems of the conventional extraction method.

In addition, by performing the step of aging the prepared ginkgo extract at 20 to 25 ° C. for 3 to 6 months to prepare the aged ginkgo extract, the wound restoration effect of trees and the growth promoting effect of trees can be greatly improved. In addition, there is an effect that can greatly improve the compatibility with the components to be described later of the coating composition for the protection and pest control of trees and wood according to an embodiment of the present invention.

At this time, after the step of preparing the ginkgo extract, the aged ginkgo extract is a mixture of the prepared ginkgo extract and gelatin-apatite sol in a weight ratio of 1: 0.1 to 3 at 20 to 25 ° C. for 3 to 6 months. By being prepared by a manufacturing method comprising the step of preparing the aged ginkgo extract by aging for a while, it is possible to further improve not only the above-described effects, but also excellent film adhesion and durability, and provide a buffer insulation effect to trees and wood. It works. Accordingly, it is possible to prevent damage to trees due to climatic disasters caused by excessive external temperature changes such as abnormal low temperature in spring and winter and abnormal high temperature in summer.

At this time, in the gelatin-apatite sol, the apatite precipitate is dispersed in the gelatin. More specifically, in consideration of the above effect, the molar ratio of [Ca]/[P] in the gelatin is in the range of 0.5 to 0.9, Ca ( NO ₃ ) ₂ ·4H ₂ O and (NH ₃ ) ₂ HPO ₄ prepared by precipitation reaction may be preferably used.

Thereafter, the content of the components described below of the coating composition for protecting trees and wood and controlling pests and pests according to an embodiment of the present invention is based on 100 parts by weight of the aged ginkgo extract.

The yeast fermented product of the flesh layer of the ginkgo biloba, ginkgo leaves and ginkgo bark serves to provide a wound restoration effect of trees, a growth promoting effect of trees, and an excellent effect of repelling diseases and pests together with the aged ginkgo extract.

In particular, ginkgo biloba is a yellow fruit of the ginkgo tree, and is composed of a succulent flesh layer (mucous outer skin), a white hard mesothelium, a brown inner endothelium of the mesoderm, and a turquoise endosperm (ginkgo berry) in the inner endosperm. . The bank fruit flesh layer jinko acid (ginkgolic acid), but only the advantage of containing and it has an antimicrobial activity or the like Mycobacterium tuberculosis, on-by that is causing the allergic skin toxicity _{(bilobol, C 21 H 34 O} 2) and toxicity However, it still contains ginkgol, which causes skin allergies, and has a unique astringent taste and a peculiar bad odor, so it is being discarded. In addition, after harvesting ginkgo nuts, in the process of separating ginkgo nuts and the pulp, which is the fleshy layer, in order to obtain ginkgo nuts, the ratio of the volume of the fruit (ginkgo nuts) to the flesh layer is about 1:4, so A large amount of fruit juice was generated along the way, resulting in a low yield, as well as a waste of resources as the fruit juice and exoskeleton contained in the flesh layer were not used and disposed of until now. The included flesh layer contaminates the water environment, and while the outer coat rots, the odor of the outer coat, which is a characteristic odor of the outer coat, is diffused into the atmosphere as it is, so there is a problem of contaminating the air environment.

In the present invention, the above-described effect can be realized by solving the problems caused by the treatment of the ginkgo berry flesh layer and recycling it.

More specifically, the yeast fermented product of the flesh layer of the ginkgo biloba, ginkgo leaves and ginkgo bark is obtained by collecting the flesh layer of ginkgo biloba, raw ginkgo leaves and ginkgo bark from the ginkgo tree, steaming and drying the ginkgo berry flesh layer. , pretreatment steps of ginkgo leaves and ginkgo bark; After mixing 1 to 5 times the weight of water with the pre-treated ginkgo meat layer, ginkgo leaves and ginkgo bark, it is heated at 110 to 180 ° C for 1 to 3 hours to extract the ginkgo meat layer, ginkgo leaves and ginkgo biloba. skin extract preparation step; Inoculating yeast mold in a liquid medium in which bran and glucose solution are mixed with the flesh layer of the ginkgo berry, ginkgo leaf and ginkgo bark extract, and culturing at 25 to 35° C. for 5 to 10 days; And after mixing a sodium phosphate buffer solution with a culture containing the extract of the flesh layer of ginkgo biloba, ginkgo leaves and ginkgo bark extract, filtration and centrifugation to obtain a supernatant, so that the yeast fermentation of the flesh layer of ginkgo biloba, ginkgo leaves and ginkgo bark What is prepared by a manufacturing method comprising; preparing water can be preferably used.

At this time, in consideration of the above-mentioned effect, the flesh layer of the ginkgo biloba, ginkgo leaves and ginkgo bark may preferably be mixed in a ratio of 1: 0.5 to 1: 0.5 to 1 by weight.

In addition, the flesh layer of the ginkgo biloba, raw ginkgo leaves and ginkgo bark are collected from the ginkgo tree, steamed and dried. Impurities can be removed.

In addition, the liquid medium in which bran and glucose solution are mixed with the flesh layer of ginkgo berry, ginkgo leaf and ginkgo bark extract is 1 to 10 parts by weight of bran and glucose in 100 parts by weight of the flesh layer of ginkgo berry, ginkgo leaf and ginkgo bark extract A mixture of 1 to 10 parts by weight of the solution may be used.

In addition, the yeast mold is Aspergillus oryzae (Aspergillus oryzae), Aspergillus awamori var kawachii (Aspergillus awamori var kawachii), Monascus ruber (Monascus ruber), Monascus purporeus (Monascus purporeus) and their One or more types selected from mixed yeast mold can be inoculated. More preferably, Aspergillus oryzae (Aspergillus oryzae) and Monascus ruber (Monascus ruber) mixed and inoculated in the same weight ratio can be preferably used.

In addition, the number of molds of yeast mold cultured in the liquid medium may be 1×10 ⁵ to 1×10 ⁷ per 1 ml.

In addition, after mixing the sodium phosphate buffer solution with a culture containing the flesh layer of the ginkgo biloba, ginkgo leaves and ginkgo bark extract, filtration and centrifugation to obtain a supernatant, the flesh layer of ginkgo biloba, ginkgo leaves and yeast of ginkgo bark In the step of preparing the fermented product, the culture medium is mixed with a sodium phosphate buffer having a concentration of 80 to 150 mM, the pH is adjusted to 7.0, left at 1 to 10° C. for 5 to 10 hours, and then the filtered filtrate is mixed with 10,000 to 15,000. It is preferably carried out by centrifugation at rpm to obtain a supernatant.

The fermented yeast of the flesh layer of the ginkgo biloba, ginkgo leaves and ginkgo bark is preferably contained in an amount of 10 to 30 parts by weight based on 100 parts by weight of the aged ginkgo juice. When the content of the fermented yeast product of the flesh layer of the ginkgo biloba, ginkgo leaves and ginkgo bark is too small, there is a problem that the above-described improvement effect may be insufficient, and yeast fermentation of the flesh layer of the ginkgo biloba, ginkgo leaves and ginkgo bark When the content of water is too large, there is a problem in that adhesion and durability of the coating film are lowered, so that it may be difficult to maintain the above-described improvement effect for a long period of time.

On the other hand, the wood vinegar is a liquid obtained by extracting smoke generated in the carbonization process of trees through a cooling device, and has a function of preventing and preventing and healing various pests including silverworms, cockroaches, rice beetles, ants, mites, etc. do.

The wood vinegar may be used without limitation as long as it is applicable to trees, but more preferably, wood vinegar of oak and chamomile can be used to further improve the above-described effect.

More specifically, the wood vinegar is a step of carbonizing the trees by applying a temperature of 800 to 1,000 ℃ after inputting 50 to 60% by weight of oak and 40 to 50% by weight of chaff wood in a loess kiln; When the smoke discharged through the flue of the loess kiln turns white, closing the kiln entrance leaving only a small vent; a liquefaction step of collecting and cooling the smoke emitted when the temperature of the flue reaches 85 to 120 °C; A step of aging the crude wood vinegar collected by liquefying the smoke in a container for at least one year at room temperature; And removing the sediment and suspended matter of the aged crude wood vinegar and filtering it with a filter to prepare an acidic wood vinegar of pH 3.5 to 4.5; it may be prepared by a manufacturing method comprising a.

The wood vinegar is preferably contained in an amount of 10 to 30 parts by weight based on 100 parts by weight of the aged ginkgo extract. When the content of the wood vinegar is too small, there is a problem that the above-mentioned improvement effect may be insufficient, and when the content of the wood vinegar is too large, the adhesion and durability of the coating film are lowered, so that it may be difficult to maintain the above-mentioned improvement effect for a long time. There is a problem.

On the other hand, the titanium dioxide powder functions to protect the wound site and prevent moisture evaporation, and to provide excellent repelling effects of various diseases and pests due to its high oxidizing power.

In addition, the titanium dioxide powder can provide a more improved buffer insulation effect to trees and wood by using a crystal structure of a rutile type having high temperature stability. In particular, when using the titanium dioxide powder having an average particle diameter of 1 to 5 μm, the refractive index is increased and the amount of light transmission is reduced, so the hiding power is excellent, which further helps to improve the buffer insulation effect.

The titanium dioxide powder is preferably contained in an amount of 5 to 25 parts by weight based on 100 parts by weight of the aged ginkgo extract. When the content of the titanium dioxide powder is too small, there is a problem that the above-described improvement effect may be insufficient, and when the content of the titanium dioxide powder is too large, the coating film adhesion and durability are lowered, and the improvement effect is maintained for a long time. There are problems that can be difficult to achieve.

On the other hand, the coating composition for protection of trees and wood and pest control provides a protective film having excellent adhesion and durability, protects wounds and prevents moisture evaporation, and provides a more excellent repelling effect of various diseases and pests, trees and wood In order to provide a better cushioning insulation effect; Based on 100 parts by weight of the aged ginkgo extract, 1 to 5 parts by weight of water-dispersed sulfur and 0.1 to 2 parts by weight of silicoaluminophosphate may be further included.

At this time, the water-dispersed sulfur is an emulsion obtained by emulsifying an organic phase containing a sulfur monomer and an aliphatic polyester-based polymer generated in the oil refining process of crude oil, and a first aqueous phase containing an effervescent salt, a second accommodation containing a hydrophilic surfactant By using the electrolyzed product after re-emulsifying with the liquid phase, the above-described effect can be further improved.

More specifically, the aqueous dispersion sulfur is 50 to 80% by volume of an organic phase containing 1 to 10% by weight of sulfur monomers, 1 to 10% by weight of an aliphatic polyester-based polymer, and the remaining amount of an organic solvent generated in the refining process of crude oil, Mixing 20 to 50% by volume of a first aqueous phase containing 5 to 30% by weight of an effervescent salt of ammonium (bi)carbonate or sodium carbonate and the remainder of distilled water to obtain a uniform W/O emulsion; and mixing the W / O emulsion with a second aqueous phase containing 0.1 to 0.5 wt % of a hydrophilic surfactant and the remaining amount of distilled water in a 1: 10 to 20 volume ratio, emulsifying, and then electrolyzing. By using the one prepared by have.

In this case, the aliphatic polyester-based polymer is at least one selected from the group consisting of poly (caprolactone), poly (valerolactone), poly (hydroxy butyrate), poly (hydroxy valerate) and mixtures thereof. It has the effect of providing a more environmentally friendly, protective film having excellent adhesion and durability.

In addition, the above-described effect may be further improved by using a mixture of methylene chloride and cyclohexyl chloride in a weight ratio of 2: 1 as the organic solvent.

In addition, the hydrophilic surfactant is a mixture of polyvinyl prorolidone and polyvinyl alcohol in a weight ratio of 1: 1, so that the above-described effect can be further improved.

In addition, the electrolysis is performed at a voltage of 220 to 380 V and a current of 10 to 100 A, thereby providing a coating film having higher stability.

On the other hand, the silicoaluminophosphate is synthesized by dissolving a block copolymer of polyethylene oxide and polypropylene oxide in an organic solvent containing alcohol to synthesize a first template solution; synthesizing a second template solution by dissolving piperidine and tetramethylammonium chloride (TMACl) in distilled water; In 100 parts by weight of a mixed template solution obtained by mixing the first template solution and the second template solution in a ratio of 1: 2 to 5 by weight, sodium silicate, pseudo-bohemite, and alkylphosphos represented by the following Chemical Formula 1 Preparing a hydrogel by mixing 20 to 50 parts by weight of a source mixture in which the phonic acid compound is mixed in an amount of 50 to 80% by weight, 15 to 45% by weight, and 1 to 10% by weight, respectively; Forming a solid product by stirring the prepared hydrogel at a temperature of 30 to 90 ℃ for 2 to 24 hours and then stirring for 5 to 48 hours at a temperature of 150 to 200 ℃ for hydrothermal reaction; and calcining the obtained solid product at a temperature of 800 to 1000 °C for 1 to 5 hours at a temperature increase rate of 0.2 to 2 °C/min, followed by slow cooling. Instead, it is possible to provide a more improved cushioning and insulation effect to trees and wood. Accordingly, it is possible to prevent damage to trees due to climatic disasters caused by excessive external temperature changes such as abnormal low temperature in spring and winter and abnormal high temperature in summer.

[Formula 1]

In the above formula, R ¹ is a linear or branched C1 to C4 alkyl group, and x is 0 or 1.

At this time, the step of dissolving the block copolymer of polyethylene oxide and polypropylene oxide in the organic solvent containing the alcohol to synthesize the first template solution is a step of synthesizing the first template solution of polyethylene oxide and polypropylene oxide in 100 parts by weight of the organic solvent containing the alcohol. It may be carried out by dissolving 1 to 10 parts by weight of the block copolymer.

In addition, the organic solvent containing the alcohol is generally used in the art, and the type thereof is not particularly limited, but, for example, an alkyl alcohol having 1 to 15 carbon atoms may be used.

In addition, the block copolymer of polyethylene oxide and polypropylene oxide has the effect of providing a first template having excellent strength even at high porosity by using a polyethylene oxide/polypropylene oxide molar ratio in the range of 0.9 to 1.1. .

Meanwhile, the step of dissolving piperidine and tetramethylammonium chloride (TMACl) in distilled water to synthesize a second template solution includes 0.1 to 5 parts by weight of piperidine and tetramethylammonium chloride (TMACl) in 100 parts by weight of distilled water. It may be carried out by dissolving 1 to 10 parts by weight.

Accordingly, by using a mixed template in which the first template and the second template having different porosity from each other are mixed, the above-described effect can be greatly improved.

In addition, the coating composition for tree and wood protection and pest control according to an embodiment of the present invention, based on 100 parts by weight of the aged ginkgo extract, a luminescent pigment, a Zion pigment, a luminescent pigment, and a mixed pigment thereof. 0.01 to 1 part by weight of one or more pigments selected from may be further included. Accordingly, it is possible to effectively represent a target sign on trees and wood, such as preventing traffic accidents at night and securing safe and secure paths for pedestrians.

On the other hand, according to the coating composition for protection of trees and wood and pest control according to an embodiment of the present invention, it provides a buffer insulation effect to trees and wood, such as abnormal low temperature phenomenon in spring and winter and abnormal high temperature in summer It has the effect of preventing damage to trees due to climatic disasters caused by excessive external temperature changes.

In addition, there is an effect that can protect the trees and wood by applying directly to the trees and wood. In particular, in the case of trees, it is possible to promote the growth of trees by inhibiting moisture evaporation by forming a protective film, and by promoting wound healing and regeneration, it has the effect of urgently restoring the wounds of trees and helping the growth of trees. .

In addition, by providing a protective film having excellent adhesion and durability, there is an effect of providing a coating film having a low loss rate of the coating film due to environmental changes after application and high stability.

In addition, the repelling effect of various pests, including silverfish, cockroaches, rice beetles, ants, mites, etc., is excellent, and this repelling effect is maintained for a long period of time, thereby protecting trees and wood from pests. In particular, unlike existing coating agent compositions, it is harmless to the human body and eco-friendly, so it is applied directly to not only domestic wood, but also various parks and city living facilities made of wood, and plantings such as street trees and fruit trees to create a comfortable indoor and outdoor environment. can have an effect.

As mentioned above, although preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various modifications can be made by those skilled in the art within the scope of the technical spirit of the present invention. This is possible.

<Preparation Example 1-1>

Preparation of Ginkgo Aging Extract

Ginkgo biloba containing stems, branches and bark was placed in a hot-pressed extractor, and the broth was purified by boiling at 200° C. for 68 hours, followed by distillation and cooling to prepare a ginkgo extract. The prepared ginkgo extract was aged at 25° C. for 4.5 months to prepare a ginkgo aged extract.

<Preparation Example 1-2>

Preparation of Ginkgo biloba juice containing gelatin-apatite sol

Ginkgo biloba containing stems, branches and bark was placed in a hot-pressed extractor, and the broth was purified by boiling at 200° C. for 68 hours, followed by distillation and cooling to prepare a ginkgo extract.

The prepared ginkgo biloba extract was mixed with gelatin-apatite sol in a weight ratio of 1: 0.5. At this time, the gelatin-apatite sol was mixed with Ca-gelatin solution and P-gelatin solution so that the molar ratio of [Ca]/[P] in gelatin was in the 0.9 range, and then the pH was adjusted to 10 using _{NH 4 OH.} While maintaining, the gelatin-apatite sol prepared by precipitating _{Ca(NO 3} ) ₂ .4H ₂ O and (NH ₃ ) ₂ HPO ₄ by stirring at a temperature of 40° C. at a speed of 500 rpm was used.

Thereafter, the mixture of the ginkgo biloba extract and gelatin-apatite sol was aged at 25° C. for 4.5 months to prepare a ginkgo biloba maturation extract containing gelatin-apatite sol.

<Production Example 2>

Manufacture of fermented yeast from the flesh layer of ginkgo berries, ginkgo leaves and ginkgo bark

Ginkgo biloba flesh layer, raw ginkgo leaves and ginkgo bark were collected from ginkgo biloba, steamed and dried to pre-treat the ginkgo biloba flesh layer, ginkgo leaves and ginkgo bark. The pre-treated ginkgo meat layer, ginkgo leaves and ginkgo bark were mixed in a weight ratio of 1: 0.8: 0.7, mixed with 3 times the weight of water in the mixture, and extracted by heating at 150 ° C. for 2 hours. of the flesh layer, ginkgo leaves and ginkgo bark extracts were prepared.

Thereafter, yeast mold was inoculated into a liquid medium in which 7 parts by weight of bran and 5 parts by weight of a glucose solution were mixed with 100 parts by weight of the ginkgo berry flesh layer, ginkgo leaf and ginkgo bark extract, and cultured at 35° C. for 7 days. At this time, the yeast mold was mixed and inoculated with Aspergillus oryzae and Monascus ruber in the same weight ratio.

Thereafter, the pH was adjusted to 7.0 by mixing a 9 mM concentration of sodium phosphate buffer with a culture containing the flesh layer of the ginkgo berry, the ginkgo leaf and the ginkgo bark extract, and left at 4° C. for 8 hours, and then the filtered filtrate was centrifuged at 13,000 rpm to obtain a supernatant, thereby preparing a yeast fermented product of the flesh layer of ginkgo nuts, ginkgo leaves and ginkgo bark.

<Example 1>

Based on 100 parts by weight of the aged ginkgo juice prepared in Preparation Example 1-1, 28 parts by weight of the yeast fermented product of the flesh layer of the ginkgo berry prepared in Preparation Example 2, ginkgo leaves and ginkgo bark; 19 parts by weight of wood vinegar; And 12 parts by weight of titanium dioxide powder was mixed to prepare a coating composition for protecting trees and wood and controlling diseases and pests.

At this time, the wood vinegar prepared in the following way was used.

First, after putting 55 wt% of oak and 45 wt% of bark wood in a loess kiln, 950 ° C. temperature was applied to carbonize the trees; When the smoke emitted through the flue of the loess kiln turns white, the kiln entrance is closed, leaving only a small ventilation hole. After that, after collecting the exhausted smoke when the temperature of the flue reaches 110 ℃ and liquefying the cooling smoke; The crude wood vinegar collected by liquefying the smoke was placed in a container and aged at room temperature for more than one year. Thereafter, the precipitate and suspension of the aged crude wood vinegar were removed and filtered through a filter, which was prepared by preparing an acidic wood vinegar of pH 4.5.

In addition, the titanium dioxide powder has a rutile-type crystal structure, and an average particle diameter of about 1.5 μm was used.

<Example 2>

It was carried out in the same manner as in Example 1, but instead of the aged ginkgo extract prepared in Preparation Example 1-1, the gelatin-apatite sol prepared in Preparation Example 1-2 was used instead of the aged ginkgo extract, A coating composition for protecting trees and wood and controlling pests was prepared.

<Example 3>

Based on 100 parts by weight of the aged ginkgo juice containing the gelatin-apatite sol prepared in Preparation Example 1-2, 28 parts by weight of the yeast fermented product of the ginkgo berry flesh layer, ginkgo leaves and ginkgo bark prepared in Preparation Example 2 ; 28 parts by weight of wood vinegar; 22 parts by weight of titanium dioxide powder; 3 parts by weight of sulfur in water; And 1 part by weight of silicoaluminophosphate was mixed to prepare a coating composition for protecting trees and wood and controlling pests.

At this time, the water-dispersed sulfur is 10 wt% of sulfur monomer generated in the crude oil refining process, and 4 wt% of an aliphatic polyester-based polymer (poly(caprolactone) and poly(valerolactone) are mixed in a 1:1 weight ratio) and 75% by volume of an organic phase containing the remaining amount of an organic solvent (methylene chloride and cyclohexyl chloride mixed in a 2: 1 weight ratio), 15% by weight of ammonium (bi)carbonate, and a balance of a first aqueous phase 25 containing distilled water After mixing the volume % to obtain a uniform W/O emulsion; The W/O emulsion is mixed with a second aqueous phase containing 0.3 wt% of a hydrophilic surfactant (polyvinyl prorolidone and polyvinyl alcohol in a 1: 1 weight ratio) and the remainder of distilled water in a 1:20 volume ratio. to emulsify; By electrolysis at a voltage of 220 V and a current of 90 A, those prepared were used.

In addition, the silicoaluminophosphate is a first template solution by dissolving 7 parts by weight of a block copolymer of polyethylene oxide and polypropylene oxide (molar ratio of polyethylene oxide / polypropylene oxide = 1.0) in 100 parts by weight of isopropyl alcohol. after; After dissolving 2 parts by weight of piperidine and 5 parts by weight of tetramethylammonium chloride (TMACl) in 100 parts by weight of distilled water to synthesize a second template solution; In 100 parts by weight of a mixed template solution obtained by mixing the first template solution and the second template solution in a 1:2 weight ratio, sodium silicate, pseudo-bohemite, and alkylphos represented by the following Chemical Formula 1-1 After preparing a hydrogel by mixing 40 parts by weight of a source mixture in which the phonic acid compound is mixed in content ranges of 70% by weight, 25% by weight and 5% by weight, respectively; After aging the prepared hydrogel by stirring at a temperature of 75 °C for 10 hours, stirring at a temperature of 180 °C for 19 hours for hydrothermal reaction to form a solid product; The obtained solid product was calcined at a temperature of 1000° C. for 2 hours at a temperature increase rate of 0.5° C./min and then slowly cooled, so that the prepared product was used.

[Formula 1-1]

In the above formula, R ¹ is a methyl group, and x is 1.

<Comparative Example 1>

Ginkgo biloba containing stems, branches and bark was placed in a hot-pressed extractor, and the broth was purified by boiling at 200° C. for 68 hours, followed by distillation and cooling to prepare a ginkgo extract.

Based on 100 parts by weight of the prepared ginkgo extract, 28 parts by weight of oak vinegar; and 12 parts by weight of titanium dioxide powder to prepare a coating composition for comparison.

<Test Example>

Evaluation of the physical properties of the coating film

Using the coating composition for protection and pest control of trees and wood prepared in Examples and the coating composition for comparison prepared in Comparative Example, applied to a test piece of 50 X 50 X 4 mm made of bamboo plywood, formed The physical properties (weather resistance, anti-fog, and peel resistance) of the coating film were evaluated, and the results are shown in Table 1 below.

At this time, as a control, the same test piece, which was not coated with any composition, was used, and the evaluation results were compared.

On the other hand, the weather resistance was performed by evaluating the state of the coating film according to the test methods of DSE-M018 and KS M 5000.

In addition, the anti-fouling property was evaluated according to the following rating table according to the test methods of KS J 3201, ASTM G21 and ISO 846. At this time, Aspergillus niger ATCC 9642, Chaetomium globosum ATCC 6205, Penioillium pinophilum ATCC 11797, Gliooledium virens ATCC 9645 and Aureobasidium pullulans ATCC 15233 were used as strains used.

[Rating Table]

Grade 0: The strain fails to grow.

Grade 1: no more than 10% growth on the specimen;

Grade 2: Growing from 10 to 30% on the specimen.

Grade 3: Growing 30 to 60% over the specimen.

Grade 4: Growing over 60% over the specimen.

In addition, the peel resistance was performed by evaluating the state of the coating film according to the test method of KS F 2160.

weather resistance Anti-American immersion peelability Example 1 after 1260 hours
No whitening, no cracks and no peeling Grade 0 0.5 mm cracking Example 2 after 1260 hours
No whitening, no cracks and no peeling Grade 0 clear Example 3 after 1260 hours
No whitening, no cracks and no peeling Grade 0 clear Comparative Example 1 after 950 hours
White night and cracks Grade 1 8 mm cracking control after 100 hours
White night and cracks 4th grade 100 mm cracking

As can be seen in Table 1, the coating composition for protection and pest control of trees and wood prepared in the above Examples has better weather resistance, anti-mildness and peeling resistance compared to the comparative coating composition prepared in Comparative Examples. It was confirmed that the storage properties were remarkably excellent.

Evaluation of pest control performance

1) Silverfish repelling performance evaluation

After applying the coating composition for protection and pest control of trees and wood prepared in the above example and the coating composition for comparison prepared in Comparative Example to the inner surface of the wardrobe maintained at 25 ° C. After leaving for one day, the area of the damaged area by silverfish was measured.

2) Cockroach repelling performance evaluation

Using the coating composition for tree and wood protection and pest control prepared in Examples and the coating composition for comparison prepared in Comparative Example, it was applied to a 50 X 50 X 4 mm specimen made of bamboo plywood.

On the other hand, 100 cockroaches in a transparent acrylic box of 1 ㎥ size provided with concentric circles of diameters 50, 60, 70, 80 and 90 cm displayed on the bottom, and a box containing each of the manufactured test pieces at the center of the concentric circles. After placing the adults, 10 hours later, the number of cockroaches located inside a concentric circle of 60 cm on the floor was measured.

3) Rice beetle repelling performance evaluation

Using the coating composition for tree and wood protection and pest control prepared in Examples and the coating composition for comparison prepared in Comparative Example, it was applied to a 50 X 50 X 4 mm specimen made of bamboo plywood.

On the other hand, 10 kg of rice was put in a rice container of 1 m 3 , and the prepared test piece was put, and then left for 100 days, and then the average number of rice worms present in 1 kg of rice was measured.

4) Evaluation of ant extermination performance

Using the coating composition for tree and wood protection and pest control prepared in Examples and the coating composition for comparison prepared in Comparative Example, it was applied to a 50 X 50 X 4 mm specimen made of bamboo plywood.

On the other hand, after placing the prepared test piece next to the dish containing 100 ml of grain syrup, a camera is installed to measure the situation with a radius of 50 cm centered on the grain, and moving at a radius of 50 cm centered on the grain for 10 days. The number of ants was measured.

The results of the repelling performance of these pests are shown in Table 2 below.

silverfish
(Damage area (㎠)) cockroach rice beetle ant Example 1 0.5 2 0 5 Example 2 0 0 0 2 Example 3 0 0 0 0 Comparative Example 1 16 15 24 78

As can be seen in Table 2, the coating composition for protection and pest control of trees and wood prepared in the above Examples compared to the coating composition for comparison prepared in Comparative Examples, silverfish, cockroaches, rice beetles and ants It was found to be very effective in eradication.

Buffer insulation performance evaluation

Using the coating composition for tree and wood protection and pest control prepared in Examples and the coating composition for comparison prepared in Comparative Example, it was applied to a 50 X 50 X 4 mm specimen made of bamboo plywood.

At this time, as a control, the same test piece, which was not coated with any composition, was used, and the evaluation results were compared.

After the test piece was placed outside in the sun, the surface temperature of the test piece was measured at 8 am and 1 pm, and the results are shown in Table 3 below.

(℃) 8 am 1:00 pm temperature difference Example 1 26.6 29.8 3.2 Example 2 25.9 28.8 2.9 Example 3 25.6 28.2 2.6 Comparative Example 1 26.9 30.5 3.6 control 27.5 32.6 5.1

As can be seen in Table 3, the coating composition for protection and pest control of trees and wood prepared in the above Example was compared with the comparative coating composition prepared in Comparative Example, and the temperature of the test body according to the external temperature change It was confirmed that the degree of increase was small. Accordingly, it was confirmed that the coating composition for protection of trees and wood and pest control prepared in Examples above exhibited excellent cushioning and insulation performance compared to the coating composition for comparison prepared in Comparative Examples.

As described above, those skilled in the art to which the present invention pertains will understand that the present invention may be implemented in other specific forms without changing the technical spirit or essential characteristics thereof. Therefore, it should be understood that all of the embodiments described above are illustrative and not restrictive. The scope of the present invention should be construed as being included in the scope of the present invention, rather than the above detailed description, all changes or modifications derived from the meaning and scope of the claims to be described later and their equivalents.

Claims (5)

Based on 100 parts by weight of the aged ginkgo juice, 10 to 30 parts by weight of the yeast fermented product of the flesh layer of ginkgo berries, ginkgo leaves and ginkgo bark; 10 to 30 parts by weight of wood vinegar; and 5 to 25 parts by weight of titanium dioxide powder as a coating composition for protection of trees and wood and pest control,
The ginkgo aged extract is
Putting ginkgo in a hot extractor, purifying the hot water solution obtained by boiling at 110 to 250° C. for 60 to 72 hours, distilling and cooling to prepare a ginkgo extract; And the prepared ginkgo extract is aged at 20 to 25 ℃ for 3 to 6 months to prepare the aged ginkgo extract; will be prepared by a manufacturing method comprising;
The yeast fermented product of the flesh layer of the ginkgo berry, ginkgo leaves and ginkgo bark
A pre-treatment step of collecting the flesh layer of ginkgo biloba, raw ginkgo leaves and ginkgo bark from the ginkgo tree, steaming and drying the ginkgo flesh layer, ginkgo leaves and ginkgo bark; After mixing 1 to 5 times the weight of water with the pre-treated ginkgo meat layer, ginkgo leaves and ginkgo bark, it is heated at 110 to 180 ° C for 1 to 3 hours to extract the ginkgo meat layer, ginkgo leaves and ginkgo biloba. skin extract preparation step; Inoculating the yeast mold in a liquid medium in which bran and glucose solution are mixed with the flesh layer of the ginkgo berry, ginkgo leaf and ginkgo bark extract, and culturing at 25 to 35° C. for 5 to 10 days; And after mixing a sodium phosphate buffer solution with a culture containing the extract of the flesh layer of ginkgo biloba, ginkgo leaves and ginkgo bark extract, filtration and centrifugation to obtain a supernatant, so that the yeast fermentation of the flesh layer of ginkgo biloba, ginkgo leaves and ginkgo bark Prepared by a manufacturing method comprising; preparing water;
After the step of preparing the ginkgo biloba extract, the aged ginkgo extract is
Prepared by a manufacturing method comprising the step of preparing the aged ginkgo extract by mixing the prepared ginkgo biloba extract with gelatin-apatite sol in a ratio of 1: 0.1 to 3 by weight at 20 to 25 ° C. for 3 to 6 months. will be;
The gelatin-apatite sol is prepared by precipitating _{Ca(NO 3} ) ₂ .4H ₂ O and (NH ₃ ) ₂ HPO ₄ so that the molar ratio of [Ca]/[P] in gelatin is in the range of 0.5 to 0.9. Coating composition for protection of trees and wood and pest control, characterized in that.
delete According to claim 1,
The wood vinegar is
After inputting 50 to 60% by weight of oak and 40 to 50% by weight of bark wood in a loess kiln, carbonizing the trees by applying a temperature of 800 to 1,000°C; When the smoke discharged through the flue of the loess kiln turns white, closing the kiln entrance leaving only a small vent; a liquefaction step of collecting and cooling the smoke emitted when the temperature of the flue is 85 to 120 °C; A step of aging the crude wood vinegar collected by liquefying the smoke in a container for at least one year at room temperature; And removing the sediment and suspended matter of the aged crude wood vinegar and filtering with a filter, to prepare an acidic wood vinegar of pH 3.5 to 4.5; Protection and pest control of trees and wood, characterized in that it is prepared by a manufacturing method comprising a liniment composition.
According to claim 1,
The coating composition for protecting the trees and wood and controlling pests is
With respect to 100 parts by weight of the aged ginkgo extract,
1 to 5 parts by weight of water-dispersed sulfur and 0.1 to 2 parts by weight of silicoaluminophosphate. A coating composition for protecting trees and wood and controlling pests.
5. The method of claim 4,
The water-dispersed sulfur is
1 to 10% by weight of sulfur monomers generated in the refining process of crude oil, 1 to 10% by weight of an aliphatic polyester-based polymer, and 50 to 80% by volume of an organic phase containing the remaining amount of an organic solvent, ammonium (bi)carbonate or sodium carbonate Mixing 5 to 30% by weight of the effervescent salt and 20 to 50% by volume of the first aqueous phase containing the remaining amount of distilled water to obtain a uniform W/O emulsion; and mixing the W / O emulsion with a second aqueous phase containing 0.1 to 0.5 wt % of a hydrophilic surfactant and the remaining amount of distilled water in a 1: 10 to 20 volume ratio, emulsifying, and then electrolyzing. prepared by;
The silicoaluminophosphate is synthesized by dissolving a block copolymer of polyethylene oxide and polypropylene oxide in an organic solvent containing alcohol to synthesize a first template solution; synthesizing a second template solution by dissolving piperidine and tetramethylammonium chloride (TMACl) in distilled water; In 100 parts by weight of a mixed template solution obtained by mixing the first template solution and the second template solution in a ratio of 1: 2 to 5 by weight, sodium silicate, pseudo-bohemite, and alkylphosphos represented by the following Chemical Formula 1 Preparing a hydrogel by mixing 20 to 50 parts by weight of a source mixture in which the phonic acid compound is mixed in an amount of 50 to 80% by weight, 15 to 45% by weight, and 1 to 10% by weight, respectively; Forming a solid product by stirring the prepared hydrogel at a temperature of 30 to 90 ℃ for 2 to 24 hours and then stirring for 5 to 48 hours at a temperature of 150 to 200 ℃ for hydrothermal reaction; and calcining the obtained solid product at a temperature of 800 to 1000 °C for 1 to 5 hours at a temperature increase rate of 0.2 to 2 °C/min, followed by slow cooling. Coating composition for protection and pest control.
[Formula 1]

In the above formula, R ¹ is a linear or branched C1 to C4 alkyl group, and x is 0 or 1.